Organic semiconducting (OSC) materials are receiving growing interest mostly due to their rapid development in the recent years and the lucrative commercial prospects of organic electronics.
One particular area of importance is organic photovoltaics (OPV). Conjugated polymers have found use in OPVs as they allow devices to be manufactured by solution-processing techniques such as spin casting, dip coating or ink jet printing. Solution processing can be carried out cheaper and on a larger scale compared to the evaporative techniques used to make inorganic thin film devices. Currently, polymer based photovoltaic devices are achieving efficiencies above 8%.
In order to obtain ideal solution-processible OSC molecules two basic features are essential, firstly a rigid π-conjugated core unit to form the backbone, and secondly a suitable functionality attached to the aromatic core unit in the OSC backbone. The former extends π-π overlaps, defines the primary energy levels of the highest occupied and lowest unoccupied molecular orbitals (HOMO and LUMO), enables both charge injection and transport, and facilitates optical absorption. The latter further fine-tunes the energy levels and enables solubility and hence processability of the materials as well as π-π interactions of the molecular backbones in the solid state.
A high degree of molecular planarity reduces the energetic disorder of OSC backbones and accordingly enhances charge carrier mobilities. Linearly fusing aromatic rings is an efficient way of achieving maximum planarity with extended π-π conjugation of OSC molecules. Accordingly, most of the known polymeric OSCs with high charge carrier mobilities are generally composed of fused ring aromatic systems and are semicrystalline in their solid states. On the other hand, such fused aromatic ring systems are often difficult to synthesize, and do also often show poor solubility in organic solvents, which renders their processing as thin films for use in OE devices more difficult. Also, the OSC materials disclosed in prior art still leave room for further improvement regarding their electronic properties.
Thus there is still a need for organic semiconducting (OSC) polymers which are easy to synthesize, especially by methods suitable for mass production, show good structural organization and film-forming properties, exhibit good electronic properties, especially a high charge carrier mobility, a good processibility, especially a high solubility in organic solvents, and high stability in air. Especially for use in OPV cells, there is a need for OSC materials having a low bandgap, which enable improved light harvesting by the photoactive layer and can lead to higher cell efficiencies, compared to the polymers from prior art.
It was an aim of the present invention to provide compounds for use as organic semiconducting materials that are easy to synthesize, especially by methods suitable for mass production, and do especially show good processibility, high stability, good solubility in organic solvents, high charge carrier mobility, and a low bandgap. Another aim of the invention was to extend the pool of OSC materials available to the expert. Other aims of the present invention are immediately evident to the expert from the following detailed description.
The inventors of the present invention have found that one or more of the above aims can be achieved by providing conjugated polymers containing one or more monomers derived from s-indacene that is fused symmetrically in each terminus with dithieno[3,2-b;2′,3′-d]thiophene (IDDTT), cyclopenta[2,1-b;3,4-b]dithiophene (IDCDT), or derivatives thereof. This was made possible by overcoming the synthetic difficulties faced when trying to make large fused ring systems. Surprisingly it was also found that these enlarged fused ring systems, and the polymers containing them, still show sufficient solubility in organic solvents, which can also be further improved by introducing alkyl or alkylidene substituents onto the indacene unit. Both the homo- and co-polymers can be prepared through known transition metal catalysed polycondensation reactions. It was also found that the polymers according to the present invention have improved planarity, leading to improved the charge mobilities. As a result the polymers of the present invention were found to be attractive candidates for solution processable organic semiconductors both for use in transistor applications and photovoltaic applications. By further variation of the substituents on the fused aromatic ring system, the solubility and electronic properties of the monomers and polymers can be further optimised.
Conjugated polymers that contain in their backbone highly fused systems as disclosed in the present invention and as claimed hereinafter have not been reported in prior art so far. GB 2 472 413 A discloses small molecule materials of the structure I as shown below. However, no polymers have been reported so far.

US 2011/166362 A1 discloses small molecules containing linearly fused polycyclic aromatic backbones as in structure II below, where one of the four groups of W, X, Y and Z has to be a substituted phenylamino group. Again, no polymers using these structures have been reported so far.
